Polyurethane foam catalysts that eliminate polyurea-containing polyol based masterbatch cure drift

ABSTRACT

In the preparation of a high resiliency polyurethane foam by reacting a polyisocyanate with a polyurea dispersion-containing polyol based masterbatch composition also containing a tertiary amine catalyst for the polyurethane reaction, the improvement for eliminating cure draft of such stored polyol compositions which comprises employing a catalyst composition consisting essentially of 
     5 to 15 wt% triethylenediamine, 
     20 to 35 wt% 4-(2-dimethylaminoethyl) morpholine, 
     20 to 35 wt% N,N,N&#39;,N&#39;-tetramethyl-1,2-diamino-2-methylpropane, 
     10 to 25 wt% bis(dimethylaminoethyl)ether, and 
     5 to 40 wt% of an N-hydroxyalkyl quaternary ammonium acid salt.

TECHNICAL FIELD

This invention relates to the amine catalysis of reactions involvingorganic polyisocyanates and polyols in the production of polyurethaneproducts.

BACKGROUND OF THE INVENTION

Manufacturers of high resiliency polyurethane foam typically usemasterbatches consisting of one or more, usually two, polyols plussilicone surfactant, water, amine catalysts and possibly organometallicsalts, blowing agent, crosslinkers, dyes or pigments and flameretardants in the manufacture of automotive seating cushions and backs.These are called the "B" side components. Depending on the size of theindividual molding plant, the respective masterbatches may be consumedin as short as 2-4 hours or as long as 4-5 days. One of the typicallyused polyol masterbatches contains an in-situ made polyurea dispersion(PUD). Masterbatches comprising a polyurea dispersion-containing polyol[PUD polyol] and utilizing an acid blocked amne catalyst package rapidlychange in reactivity when used over several days. Typically afterseveral hours storage, this reactivity drift becomes apparent.Accordingly, very large volume users who consume a masterbatch over a2-4 hour period never exceed the original initiation period whereas lowto moderate volume molders generally will consume their masterbatchesover 2-4 days experiencing the cure drift problem.

Stoichiometrically, one isocyanate group is required to react with oneactive hydrogen group in the polyurethane reaction. In practice, aslight excess of the isocyanate is used to react with water to generatecarbon dioxide to expand the mixture into a foam. The ratio ofisocyanate to active hydrogen is referred to as the "isocyanate index".

Molders typically run between 95-105 isocyanate index in producing theirseating foam holding to a preselected level±one isocyanate index unit.If the index drops significantly below the selected value, the foam isundercured with poor initial and somewhat dminished final physicalproperties. If the index is greater than about 110, the foam develops ahard "boardy" feel and loses its resiliency. Both results arecommercially unacceptable.

When the PUD polyol masterbatch is used, the isocyanate index drops fromthe selected index value of typically 102±1 to the 80-85 or lower rangeafter 8 hours. In order to maintain uniform production, the polyurethanemolders must continuously add more isocyanate to hold the selected indexrange. This increases the molder's cost to produce commerciallyacceptable foam.

All polyurethane foamers, regardless of size, require a slight delay of2-3 seconds in foam initiation to allow the molds to close before thefoam rises over the mold part line. Typically, this delay is achieved byusing an acid blocked catalyst package.

The PUD polyol supplier recommends to the foam molders that non-acidblocked catalysts be used as a means of ameliorating the PUD polyolmasterbatch cure drift. This approach, however, causes the molder otherproblems. If catalyst levels are used to provide a molded foam piecethat is sufficiently cured to remove from the mold without tearing oraccepting handling marks on the surface, the foam forming reaction issufficiently advanced at mold closure to have the fresh rising foam flowover the part line. Also, the mold lid typically contains inserts whichare driven into the rising foam during closure inducing stresses andshear collapse. The overflow reduces the physical strength of theresulting foam product and wastes material. The shear collapse alsoreduces the physical properties, quality and durability of the curedfoam product.

The alternate procedure of undercatalyzing the B-side producesundercured parts that lack sufficient integrity to be easily removedfrom the mold without tearing or accepting surface imprints. If the tearis either large enough or in a critical area, the part must be scrapped.If the tear is minor or in a non-critical area, it can be repaired.However, the molder incurs an economic penalty.

U.S. 4,582,861 discloses a method for preparing polyurethane product bythe reaction of an organic polyisocyanate with a polyester or polyetherpolyol in the presence of a catalytically effective amount of a catalystsystem consisting essentially of a tertiary amine and 1-35 wt %, basedon the tertiary amine, of an N-hydroxyalkyl quaternary ammonium salt.

SUMMARY OF THE INVENTION

The present invention provides a method for substantially eliminatingcure drift in polyurea dispersion containing polyol based masterbatches.High resiliency polyurethane foam is prepared by reacting an organicpolyisocyanate component with a masterbatch containing a PUD polyolcomponent which also includes a tertiary amine catalyst for the reactionof the isocyanate with an active hydrogen moiety. The improvement forsubstantially eliminating the cure drift comprises employing a catalystcomposition consisting essentially of

(a) 5 to 15 wt % triethylenediamine,

(b) 20 to 35 wt % 4-(2-dimethylaminoethyl) morpholine,

(c) 20 to 35 wt % N,N,N',N'-tetramethyl-1,2-diamino-2-methyl propane,

(d) 10 to 25 wt % bis(N,N-dimethylaminoethyl) ether, and

(e) 5 to 40 wt % of a N-hydroxyalkyI quaternary ammonium acid saltprepared by reacting an amine of the formula ##STR1## wherein R, R₁ andR₂ are alkyl or hydroxyalkyl groups of 1-20 carbon atoms, or cycloalkylgroups of 3-8 carbon atoms, aralkyl, aryl, alkenyl groups of 2-20 carbonatoms or alkynyl groups of 2-6 carbon atoms; or R, R₁ and R₂ togetherwith the nitrogen atom constitute a N-substituted heterocyclic 5-7 atomring.

with an alkylene oxide of 2-4 carbon atoms in the presence of an acid.

The use of such catalyst composition according to the invention for themanufacture of high resiliency polyurethane foam provides the followingadvantages:

Sufficient delay in the start of the foam forming reactions to allow themolds to be closed,

Impart stability to the rising foam so that the mold is completelyfilled with good quality foam,

Impart sufficient cure to easily remove the foam at the end of the cyclewithout tearing or surface marring during removal,

Maintain a constant reactivity profile obviating the need to constantlyadjust the isocyanate index, and

Maintain these characteristics over the life of the PUD polyolmasterbatch.

DETAILED DESCRIPTION OF THE INVENTION

The preparation of high resiliency polyurethane foam product accordingto the invention uses the polyisocyanates well known in the art formaking such foams including hexamethylene diisocyanate, phenylenediisocyanate, toluene diisocyanate and 4,4'-diphenylmethanediisocyanate. Especially suitable are the 2,4- and 2,6-toluenediisocyanates ("TDI") individually or together as their commerciallyavailable mixtures. Other suitable mixtures of diisocyanates are thoseknown commercially as "crude MDI", also known as PAPI. which containabout 60% of 4,4'-diphenylmethane diisocyanate along with other isomericand analogous higher polyisocyanates. Mixtures of TDI and MDI areespecially suitable for use. Also suitable are "prepolymers" of thesepolyisocyanates comprising a partially prereacted mixture ofpolyisocyanates and polyether or polyester polyol.

Regarding the polyol component of the "B-side" masterbatch in thepreparation of high resiliency polyurethane foam, at least one polyol isa PUD polyol such as Multranol E-9151 marketed by Mobay ChemicalCorporation, and other similar PUD polyols well known in the art. Inaddition, the B-side masterbatch can also contain other polyalkyleneether or polyester polyols typically used to make high resiliency foam.The polyalkylene ether polyols include the poly(alkyleneoxide) polymerssuch as poly(ethyleneoxide) and poly(propyleneoxide) polymers andcopolymers with terminal hydroxyl groups derived from polyhydriccompounds including diols and triols, for example, among others,ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol,1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,pentaerythritol, glycerol, diglycerol, trimethylolpropane,cyclohexanediol and like low molecular weight polyols.

Useful polyester polyols include those produced by reacting adicarboxylic acid with an excess of a diol, for example, adipic acidwith ethylene glycol or butanediol, or reacting a lactone with an excessof a diol such as a caprolactone and propylene glycol.

Other typical agents found in high resiliency polyurethane foamformulations include blowing agents such as water, methylene chloride,trichlorofluoromethane and the like, and cell stabilizers such assilicones.

A general high resiliency polyurethane foam formulation would comprisethe following:

    ______________________________________                                        HIGH RESILIENCY FOAM FORMULATION                                              COMPONENT            pbw                                                      ______________________________________                                        PUD POLYOL           20 to 80                                                 POLYETHER POLYOL     20 to 80                                                 CELL STABILIZER      1 to 2.5                                                 ORGANOMETALLIC CATALYST                                                                            0 to 0.01                                                BLOWING AGENT        0 to 10                                                  INVENTION CATALYST   0.5 to 1                                                 ISOCYANATE PREPOLYMER,                                                                             95-105 INDEX, 18-22%                                     FREE NCO %                                                                    ______________________________________                                    

The polyol masterbatch, or B-side masterbatch, would comprise the firstsix listed components. The most important component with regard tosubstantially eliminating the reactivity drift is the catalystcomposition which consists essentially of

(a) 5 to 15 wt %, preferably 6 to 12 wt %, triethylenediamine,

(b) 20 to 35 wt %, preferably 22 to 32 wt %, 4-(2-dimethylaminoethyl)morpholine,

(c) 20 to 35 wt %, preferably 22 to 32 wt %,N,N-dimethyl-N',N'-dimethyl-1,2-diamino-2-methyl propane,

(d) 10 to 25 wt %, preferably 10 to 20 wt %, bis(N,N-dimethylaminoethyl)ether, and

(e) 5 to 40 wt %, preferably 15 to 35 wt %, of a N-hydroxyalkylquaternary ammonium salt.

The N-hydroxyalkyl quaternary ammonium salt is prepared by reacting atertiary amine of the following general formula ##STR2## wherein R, R₁and R₂ are independently alkyl or hydroxyalkyl groups of 1-20 carbonatoms or cycloalkyl groups of 3-8 carbon atoms, aralkyl, aryl, alkenylgroups of 2-20 carbon atoms or alkynyl groups of 2-6 carbon atoms, or R,R₁ and R₂ together with a nitrogen atom form an N-substitutedheterocyclic 5-7 atoms ring structure, examples of which includetriethylenediamine, methyltriethylenediamine, quinuclidine,N-methylmorpholine, N-ethylmorpholine, N,N'-dimethylpiperazine and1,8-diazobicyclo (5,4,0)-undecene-7.

In addition to the heterocyclic amines just mentioned, other suitabletertiary amines for making the quaternary ammonium salt includetrimethylamine, dimethylethylamine, N-dimethyl-N-hydroxyethylamine,N-benzyl-N-dimethylamine, bis(N,N-dimethylaminopropyl)-N-methylamine,N-di(hydroxyethyl)-N-phenylamine, triethanolamine,N-cyclohexyl-N-dimethylamine, and bis(dimethylaminoethyl) ether. Thepreferred tertiary amine is triethylenediamine (TEDA).

The selected tertiary amine is reacted with an alkylene oxide containing2-22 carbon atoms in the presence of an acid H-A, including inorganicand organic acids.

The alkylene oxides that can be reacted with the tertiary amine can berepresented by the general formula ##STR3## where: R₃ is hydrogen,phenyl, an alkyl group of 1-15 carbon atoms, a hydroxyalkyl group of 1-9carbon atoms or an alkoxyalkyl group having a total of 2-20 carbonatoms.

Among the particular alkylene oxides that can be reacted with thetertiary amine there are included ethylene oxide, propylene oxide,styrene oxide, glycidol and longer chain alkylene oxides. Ethylene oxideand especially propylene oxide are preferred.

It is preferred that any one of a large variety of organic acidsrepresented by the following formula may be used to furnish the anion ofthe desired N-hydroxyalkyl quaternary ammonium salt:

    Y--(O).sub.a --CO.sub.2 H

where:

a is 0 or 1,

Y is hydrogen, an alkyl group of 1-20 carbon atoms, an alkenyl group of2-15 carbon atoms, a cycloalkyl group of 3-6 carbon atoms, phenyl, analkylphenyl group having 1-9 carbon atoms in the alkyl group or groupsattached to the phenyl ring, benzyl, an alkylbenzyl having 1-9 carbonatoms in the alkyl group or groups attached to the benzene ring, or a

    --CH(.sub.3-b)Z.sub.b group

where:

b is 1-3 and

Z is --OH, --CN, --Cl, an alkoxy group of 1-5 carbon atoms, a phenylgroup or methoxyphenyl group, or

Z is --(CH₂)_(d) COOR₄ wherein d is 0-4 and R₄ is hydrogen or an alkylgroup of up to 20 carbon atoms.

The preferred quaternary ammonium carbonylate salts for use in thecatalyst composition are those in which the acid is an organiccarboxylic acid corresponding to the following general formula R₈ --CO₂H where R₈ is hydrogen, an alkyl group of 1-18 carbon atoms, an alkenylgroup of 2-15 carbon atoms, benzyl or -CH₂ CN.

Organic carboxylic acids of the above formula include short to longchain fatty acids; substituted aliphatic acids and aromatic carboxylicacids. Representative acids include formic, acetic, hexanoic, straightand branched heptanoic, octanoic, decanoic and hexadecanoic acids;neoacids such as 3,3-dimethylbutanoic acid; unsaturated aliphatic acidsuch as oleic, acrylic, methacrylic, undecenoic; aromatic acid such asbenzoic, phenylacetic and salicylic; and cyanoacetic and chloroaceticacids.

The preferred route for the preparation of the hydroxyalkyl quaternaryammonium salts used in the invention is by reaction of the appropriatetertiary amine with an alkylene oxide in the presence of the chosenacid. If the corresponding ammonium compound is commercially availableas the hydroxide or alkoxide, formation of the desired salt can bedirectly obtained by reaction of the quaternary ammonium base with thedesired acid.

Preparation of the hydroxyalkyl quaternary ammonium salts is more fullydescribed in U.S. 4,040,992 and 4,582,861 which are incorporated byreference.

In the usual method of preparation of the desired hydroxyalkyl ammoniumquaternary salts, equivalent amounts of the tertiary amine, thecarboxylic acid and an alkylene oxide are mixed, preferably in thepresence of a suitable solvent such as dipropylene glycol, ethyleneglycol or 1,4-butanediol. The alkylene oxide may be used in excessamounts ranging from 0 to about 200% excess on a molar basis, especiallya 100% molar excess when triethylenediamine is used. The reaction iscarried out at a temperature in a range of 25-60° C. and at aboutatmospheric pressure, although higher pressures may be employed, ifdesired.

Hydroxypropylated triethylenediamine quaternary salts of formic acid andcarboxylic acids having up to about 10 carbon atoms such as those of2-ethylhexanoic and various decanoic acids are preferred. The preferredhydroxypropylated triethylenediamine quaternary salts are those preparedby reacting triethylenediamine with 2 molar equivalents of the alkyleneoxide in the presence of the chosen acid.

In the usual method of preparation. the alkylene oxide is used in excessof equimolar amounts with triethylenediamine, desirably in amountsranging from 30 to about 200% excess on a molar basis, especially about100% molar excess.

A catalytically effective amount of the catalyst composition of theinvention is used in the high resiliency polyurethane foam formulation.More specifically, suitable amounts of the catalyst composition mayrange from about 0.1 to 3 parts per 100 parts polyol in the polyurethaneformulations.

EXAMPLE 1

The following general procedure for the preparation of the carboxylicacid salt of hydroxypropylated triethylenediamine is essentially astaught in U.S. 4,040,992 except that greater than an equimolar quantityof the alkylene oxide is used.

A suitable amount of glycol solvent is charged to a reaction vesselequipped with a stirrer, dropping funnel, condenser and heating mantle.One mole of the appropriate carboxylic acid (144 g for 2-ethylhexanoicacid) is added. The reaction vessel is surrounded with a cooling bath(about 15° C.) and one mole of the amine (112 g triethylenediamine) isadded. The reaction temperature is allowed to reach 25° C. whereupon 2moles of alkylene oxide (116 g propylene oxide) is added to the reactionmixture. Although the reaction is exothermic, it may be controlled bythe slow addition of the alkylene oxide. After all the alkylene oxidehas been added, the reaction temperature is maintained at about 40° C.for a period of time. preferably about 30 minutes.

All evaluations of catalyst compositions were done with the followingfoam formulation:

    ______________________________________                                        FOAM FORMULATION                                                                                  pbw                                                       ______________________________________                                        MULTRANOL E-9151.sup.a 28 ± 2 OH #                                                               50                                                      MULTRANOL E-3901.sup.b 28 ± 2 OH #                                                               50                                                      DC-5043.sup.c         1.75                                                    UL-1.sup.d (10% in DOP)                                                                             0.08                                                    WATER                 4.5                                                     MONDUR E-531.sup.e    VARIOUS                                                                       INDEXES                                                 ______________________________________                                         .sup.a A 6000 mol wt triol containing approximately 22-25 wt % of a           polyurea dispersion and having a hydroxyl number of 28 ± 2 marketed by     Mobay Chemical Corp.                                                          .sup.b A 6000 mol wt triol having a hydroxyl number of 28 ± 2 marketed     by Mobay Chemical Corp.                                                       .sup.c A silicone cell stabilizer marketed by Dow Corning Corp.               .sup.d An organometallic catalyst marketed by Witco Corp.                     .sup.e A blend of toluene diisocyanate and 4,4diphenylmethane diisocyanat     by Mobay Chemical Corp.                                                  

The masterbatch instability (cure drift) was determined by comparingfoam made from a fresh masterbatch to foam made from the samemasterbatch aged 2 days at 120° F. (48.9° C.) Two days at 120° F.produced essentially equivalent results to masterbatch aged 16 days atambient temperature. In addition, 120° F. was the highest observedtemperature encountered by a mold producer.

The key parameters measured were cream time, top-of-cup and string gel.

"Cream time" is the time in seconds from the start of mixing thecatalyzed masterbatch and isocyanate to the onset of rise in themixture. This parameter is a measure of the time to the commencement ofthe foaming reaction.

"Top-of-cup" is the time in seconds from the start of mixing thecatalyzed masterbatch and isocyanate to the rise of the foam to the topof a 5 quart cup. This parameter is a measure of foam rise rate.

"String gel" is the time in seconds from the start of mixing thecatalyzed masterbatch and isocyanate to the time a string of reactionproduct is pulled from the foam when a rod is placed in the foam andremoved. This parameter is a measure of the degree of the polymerizationreaction and indicates the resulting foam has developed sufficientstrength to maintain its integrity.

An added constraint based on the correlation of hand mixed foams toproduction requirements is that the cream time must exceed 10 seconds inorder to permit the molds to close before the foam overflows the moldcavity part line.

A base catalyst blend (BCB) known to produce commercially acceptablehigh resiliency foam was used as the comparative starting point. The BCBcomprised the following:

    ______________________________________                                        BASE CATALYST BLEND                                                                                wt %                                                     ______________________________________                                        4-(2-dimethylaminoethyl) morpholine                                                                  27.3                                                   N,N,N',N'--tetramethyl-1,2-diamino-2-                                                                27.3                                                   methylpropane                                                                 Bis(dimethylaminoethyl) ether                                                                        12.7                                                   Triethylenediamine      9.1                                                   Dipropylene glycol     23.6                                                   ______________________________________                                    

EXAMPLE 2

In this example, the BCB was evaluated with various levels of formicacid. (See Table 1). At the lowest levels, the change in cure time after16 days storage was marginally acceptable (6%), but the initiationoccurred too fast to permit mold closure before the foam overflowed themold. As the formic acid level was increased to achieve the proper delayin foam initiation, the cure drift as shown by Run 2 approached 15%which is totally unacceptable. Run 5 is a commercially used acid blockedcatalyst blend that illustrates cure drift.

                                      TABLE 1                                     __________________________________________________________________________    EFFECT OF FORMIC ACID LEVELS                                                  AMBIENT TEMPERATURE                                                           DAYS           INITIATION                                                                            TOP OF CUP                                                                            STRING GEL                                     RUN CATALYST                                                                              PHP                                                                              0   16  0   16  0   16                                         __________________________________________________________________________    1   BCB +   0.85                                                                             13  15  62  75  85  94                                             0.088 php FA                                                              2   BCB +   0.85                                                                             11  13  56  64  78  86                                             0.063 php FA                                                              3   BCB +   0.85                                                                             10  12  46  54  69  73                                             0.038 php FA                                                              4   BCB +   0.65                                                                              9   9  39  39  60  59                                             0.0 PHP FA                                                                5   Dabco ® 8154/                                                                     0.70                                                                             12  13  53  69  78  95                                             Polycat ® 77/                                                             Dabco BL-11/                                                                  Dabco 33LV                                                                __________________________________________________________________________

EXAMPLE 3

In this example, the PUD polyol masterbatch containing the BCB with andwithout acid blocking were evaluated after storage at 120° F. It can beseen from the data in Table 2 that Run 6 and Run 7 in which the BCBcontaining masterbatch with and without acid blocking, respectively,showed 36 and 23% drift in cure rates, respectively. The same BCB withthe acid blocking added to the catalyst composition just before use wasmixed with aged masterbatches (Run 8) and exhibited essentially nocharge in cure. From this data it can be concluded that acid blocking isnot the only cure of the cure change.

                                      TABLE 2                                     __________________________________________________________________________    ACCELERATED AGING STUDY                                                       120° F.                                                                              INITIATION (SEC)                                                                         TOP OF CUP (SEC)                                                                         STRING GEL (SEC)                          RUN DAYS AT 120° F.                                                                  0  2 4  8  0 2  4  8  0 2  4  8                                 __________________________________________________________________________    6   BCB + 12% FA                                                                            15 14                                                                              13 14 64                                                                              93 92 93 90                                                                              123                                                                              122                                                                              122                               7   BCB W/O ACID                                                                             9 11                                                                              10 10 36                                                                              46 45 45 56                                                                              69 67 64                                8   BCB (ACID  9  9                                                                               9  9 37                                                                              38 42 40 58                                                                              57 64 59                                    POST ADDED)                                                               __________________________________________________________________________

This example shows the results obtained using the BCB with 30% ofvarious N-hydroxypropyl quaternary ammonium salts. It can be seen fromthe data in Table 3 that incorporation of an amount of anN-hydroxypropyl quaternary ammonium salt yielded sufficient delay incream time. In fact, the use of a quaternary ammonium product from thereaction of TEDA (1 mole), propylene oxide (2 moles) and 2-ethylhexanoicacid (1 mole) in combination with the BCB provided a catalyst system inwhich the initiation tion was sufficiently delayed to permit the mold tobe closed without overflowing and significantly retarded the masterbatchcure drift.

                                      TABLE 3                                     __________________________________________________________________________    AMBIENT TEMPERATURE                                                           DAYS              INITIATION                                                                            TOP OF CUP                                                                            STRING GEL                                  RUN CATALYST   PHP                                                                              0   16  0   16  0   16                                      __________________________________________________________________________     9  BCB + .23 MOLES                                                                          0.85                                                                             13  15  62  75  85  94                                          FA                                                                        10  BCB + NTQ1 0.68                                                                             10  12  54  70  78  95                                      11  BCB + NTQ2 0.68                                                                             11  14  49  65  68  85                                      12  BCB + NTQ3 0.68                                                                             10  11  47  56  70  76                                      __________________________________________________________________________     NTQ1 is the reaction product of trimethylamine, propylene oxide and           cyanoacetic acid in equimolar amounts.                                        NTQ2 is the reaction product of dimethylethanolamine, propylene oxide and     formic acid in equimolar amounts.                                             NTQ3 is the reaction product of 1 mole TEDA, 2 moles propylene oxide and      mole 2ethylhexanoic acid as a 50% solution in ethylene glycol.           

EXAMPLE 5

In this example, the catalyst of Run 12 was reformulated so that twoparts of BCB was used in combination with one part of the hydroxypropylquaternary ammonium salt in an accelerated aging test. Again, it can beseen from the data in Table 4 that this particular combination of activecomponents (Run 14) provides a catalyst composition eminently suited forPUD polyol masterbatches. Run 15 shows a commercial catalyst blend forhigh resiliency foam. Although Run 15 appears to solve the cure driftproblem, the total cure time for the finished product (not shown inTable 4) was deficient compared to Run 14.

                                      TABLE 4                                     __________________________________________________________________________    ACCELERATED AGING AT 120° F.                                           DAYS              INITIATION                                                                            TOP OF CUP                                                                            STRING GEL                                  RUN CATALYST   PHP                                                                              0   16  0   16  0   16                                      __________________________________________________________________________    13  BCB + .23 MOLES                                                                          0.85                                                                             13  13  56  70  76  96                                          FA                                                                        14  2 BCB + 1 NTQ3                                                                           0.60                                                                             10  11  53  58  74  84                                      15  Polycat 77/                                                                              0.50                                                                             10  11  56  62  82  86                                          NIAX A-4/                                                                     DABCO BL-11                                                               __________________________________________________________________________

Thus, the invention provides a catalyst composition for a masterbatchthat reacts uniformly over its existence, namely 2-4 days. The catalystcomposition works because it

(a) delays the initiation of the foam forming reactions sufficiently topermit mold closure without the foam spilling over the sides of thebottom half of the mold.

(b) maintains the stability of the rising foam in the mold as it flowsthrough the internal restrictions,

(c) produces a sufficient degree of cure throughout the foam to permitremoval without tearing or accepting finger printing on the surface,

(d) maintains a constant reactivity profile so that the operator doesnot have to constantly adjust the amount of isocyanate to be added toachieve the desired final physical properties, and

(e) maintains these characteristics over the life of the masterbatch.

STATEMENT OF INDUSTRIAL APPLICATION

The invention provides a catalyst composition for polyureadispersion-containing polyol masterbatches in the preparation of highresiliency polyurethane foam which inhibits the loss in reactivity ofthe masterbatch with storage.

We claim:
 1. In a method for preparing a high resiliency polyurethanefoam by the reaction of a polyisocyanate with a polyureadispersion-containing polyol based masterbatch composition alsocontaining an amine catalyst for the polyurethane reaction, theimprovement which comprises employing as the catalyst a compositionconsisting essentially of(a) 5 to 15 wt % triethylenediamine, (b) 20 to35 wt % 4-(2-dimethylaminoethyl) morpholine, (c) 20 to 35 wt %N,N,N',N'-tetramethyl-1,2-diamino-2-methylpropane, (d) 10 to 25 wt %bis(N,N-dimethylaminoethyl) ether, and (e) 5 to 40 wt % of aN-hydroxyalkyl quaternary ammonium acid salt prepared by reacting anamine of the formula ##STR4## where R, R₁ and R₂ are independently alkylor hydroxyalkyl alkyl groups of 1-20 carbon atoms, cycloalkyl groups of3-8 carbon atoms, aralkyl, aryl, alkenyl groups of 2-20 carbon atoms oralkynyl groups of 2-6 carbon atoms, orR, R₁ and R₂ together with anitrogen atom form an N-substituted heterocyclic 5-7 atoms ringstructure, with an alkylene oxide having 2-22 carbon atoms in thepresence of an acid.
 2. The method of claim 1 in which R, R₁ and R₂ areindependently alkyl or hydroxyalkyl groups of 1-20 carbon atoms.
 3. Themethod of claim 1 in which the amine used in preparing theN-hydroxyalkyl quaternary ammonium acid salt is triethylenediamine. 4.The method of claim 1 in which the amine used in preparing theN-hydroxyalkyl quaternary ammonium acid salt is dimethylethanolamine. 5.The method of claim 1 in which the amine used in preparing theN-hydroxyalkyl quaternary ammonium acid salt is trimethylamine.
 6. Themethod of claim 1 in which the alkylene oxide is ethylene oxide orpropylene oxide.
 7. The method of claim 1 in which the acid is formicacid.
 8. The method of claim 1 in which the acid is cyanoacetic acid. 9.The method of claim 1 in which the acid is 2-ethylhexanoic acid.
 10. Ina method for preparing a high resiliency polyurethane foam by thereaction of a polyisocyanate with a polyurea dispersion-containingpolyol based masterbatch composition also containing an amine catalystwith the polyurethane reaction, the improvement which comprisesemploying as the catalyst a composition consisting essentially of(a) 6to 12 wt % triethylenediamine, (b) 22 to 32 wt %4-(2-dimethylaminoethyl) morpholine, (c) 22 to 32 wt %N,N,N',N'-tetramethyl-1,2-diamino-2-methylpropane, (d) 10 to 20 wt %bis(N,N-dimethylaminoethyl ether, and (e) 15 to 35 wt % of aN-hydroxyalkyl quaternary ammonium acid salt prepared by reactingtriethylenediamine with ethylene oxide or propylene oxide in thepresence of an organic carboxylic acid of the formula R where R₈ CO₂ Hwhere R₈ is hydrogen, an alkyl group of 1-18 carbon atoms, an alkenylgroup of 2-15 carbon atoms, benzyl or --CH₂ CN.
 11. The method of claim10 in which propylene oxide is used in the preparation of theN-hydroxyalkyl quaternary ammonium salt.
 12. The method of claim 11 inwhich 2 moles of triethylenediamine is reacted with 1 mole of propyleneoxide in the presence of 1 mole of an organic carboxylic acid.
 13. Themethod of claim 12 in which the organic carboxylic acid is2-ethylhexanoic acid.